PhaseCombo_Interaction is a derived class of GibbsExcessVPSSTP that employs the Margules approximation for the excess Gibbs free energy while eliminating the entropy of mixing term. More...
#include <PhaseCombo_Interaction.h>
Public Member Functions | |
| PhaseCombo_Interaction () | |
| Constructor. More... | |
| PhaseCombo_Interaction (const std::string &inputFile, const std::string &id="") | |
| Construct and initialize a PhaseCombo_Interaction ThermoPhase object directly from an XML input file. More... | |
| PhaseCombo_Interaction (XML_Node &phaseRef, const std::string &id="") | |
| Construct and initialize a PhaseCombo_Interaction ThermoPhase object directly from an XML database. More... | |
Utilities | |
| virtual std::string | type () const |
| String indicating the thermodynamic model implemented. More... | |
Molar Thermodynamic Properties | |
| virtual doublereal | enthalpy_mole () const |
| Molar enthalpy. Units: J/kmol. More... | |
| virtual doublereal | entropy_mole () const |
| Molar entropy. Units: J/kmol/K. More... | |
| virtual doublereal | cp_mole () const |
| Molar heat capacity at constant pressure. Units: J/kmol/K. More... | |
| virtual doublereal | cv_mole () const |
| Molar heat capacity at constant volume. Units: J/kmol/K. More... | |
Activities, Standard States, and Activity Concentrations | |
The activity \(a_k\) of a species in solution is related to the chemical potential by \[ \mu_k = \mu_k^0(T) + \hat R T \log a_k. \] The quantity \(\mu_k^0(T,P)\) is the chemical potential at unit activity, which depends only on temperature and pressure. | |
| virtual void | getActivityCoefficients (doublereal *ac) const |
| Get the array of non-dimensional molar-based activity coefficients at the current solution temperature, pressure, and solution concentration. More... | |
Partial Molar Properties of the Solution | |
| virtual void | getChemPotentials (doublereal *mu) const |
| Get the species chemical potentials. Units: J/kmol. More... | |
| virtual void | getPartialMolarEnthalpies (doublereal *hbar) const |
| Returns an array of partial molar enthalpies for the species in the mixture. More... | |
| virtual void | getPartialMolarEntropies (doublereal *sbar) const |
| Returns an array of partial molar entropies for the species in the mixture. More... | |
| virtual void | getPartialMolarCp (doublereal *cpbar) const |
| Returns an array of partial molar entropies for the species in the mixture. More... | |
| virtual void | getPartialMolarVolumes (doublereal *vbar) const |
| Return an array of partial molar volumes for the species in the mixture. More... | |
| virtual void | getd2lnActCoeffdT2 (doublereal *d2lnActCoeffdT2) const |
| Get the array of temperature second derivatives of the log activity coefficients. More... | |
| virtual void | getdlnActCoeffdT (doublereal *dlnActCoeffdT) const |
| Get the array of temperature derivatives of the log activity coefficients. More... | |
Initialization | |
The following methods are used in the process of constructing the phase and setting its parameters from a specification in an input file. They are not normally used in application programs. To see how they are used, see importPhase(). | |
| virtual void | initThermo () |
| virtual void | initThermoXML (XML_Node &phaseNode, const std::string &id) |
| Import and initialize a ThermoPhase object using an XML tree. More... | |
Derivatives of Thermodynamic Variables needed for Applications | |
| virtual void | getdlnActCoeffds (const doublereal dTds, const doublereal *const dXds, doublereal *dlnActCoeffds) const |
| Get the change in activity coefficients wrt changes in state (temp, mole fraction, etc) along a line in parameter space or along a line in physical space. More... | |
| virtual void | getdlnActCoeffdlnX_diag (doublereal *dlnActCoeffdlnX_diag) const |
| Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only. More... | |
| virtual void | getdlnActCoeffdlnN_diag (doublereal *dlnActCoeffdlnN_diag) const |
| Get the array of log species mole number derivatives of the log activity coefficients. More... | |
| virtual void | getdlnActCoeffdlnN (const size_t ld, doublereal *const dlnActCoeffdlnN) |
| Get the array of derivatives of the log activity coefficients with respect to the log of the species mole numbers. More... | |
 Public Member Functions inherited from GibbsExcessVPSSTP | |
| GibbsExcessVPSSTP () | |
| virtual void | getActivityConcentrations (doublereal *c) const |
| This method returns an array of generalized concentrations. More... | |
| virtual doublereal | standardConcentration (size_t k=0) const |
| The standard concentration \( C^0_k \) used to normalize the generalized concentration. More... | |
| virtual doublereal | logStandardConc (size_t k=0) const |
| Natural logarithm of the standard concentration of the kth species. More... | |
| virtual void | getActivities (doublereal *ac) const |
| Get the array of non-dimensional activities (molality based for this class and classes that derive from it) at the current solution temperature, pressure, and solution concentration. More... | |
| virtual void | getdlnActCoeffdlnX (doublereal *dlnActCoeffdlnX) const |
| Get the array of log concentration-like derivatives of the log activity coefficients. More... | |
| virtual const vector_fp & | getPartialMolarVolumesVector () const |
| virtual bool | addSpecies (shared_ptr< Species > spec) |
| Public Member Functions inherited from VPStandardStateTP | |
| VPStandardStateTP () | |
| Constructor. More... | |
| virtual int | standardStateConvention () const |
| This method returns the convention used in specification of the standard state, of which there are currently two, temperature based, and variable pressure based. More... | |
| virtual void | getChemPotentials_RT (doublereal *mu) const |
| Get the array of non-dimensional species chemical potentials. More... | |
| virtual void | getStandardChemPotentials (doublereal *mu) const |
| Get the array of chemical potentials at unit activity for the species at their standard states at the current T and P of the solution. More... | |
| virtual void | getEnthalpy_RT (doublereal *hrt) const |
| Get the nondimensional Enthalpy functions for the species at their standard states at the current T and P of the solution. More... | |
| virtual void | getEntropy_R (doublereal *sr) const |
| Get the array of nondimensional Entropy functions for the standard state species at the current T and P of the solution. More... | |
| virtual void | getGibbs_RT (doublereal *grt) const |
| Get the nondimensional Gibbs functions for the species in their standard states at the current T and P of the solution. More... | |
| virtual void | getPureGibbs (doublereal *gpure) const |
| Get the Gibbs functions for the standard state of the species at the current T and P of the solution. More... | |
| virtual void | getIntEnergy_RT (doublereal *urt) const |
| Returns the vector of nondimensional Internal Energies of the standard state species at the current T and P of the solution. More... | |
| virtual void | getCp_R (doublereal *cpr) const |
| Get the nondimensional Heat Capacities at constant pressure for the species standard states at the current T and P of the solution. More... | |
| virtual void | getStandardVolumes (doublereal *vol) const |
| Get the molar volumes of the species standard states at the current T and P of the solution. More... | |
| virtual const vector_fp & | getStandardVolumes () const |
| virtual void | setTemperature (const doublereal temp) |
| Set the temperature of the phase. More... | |
| virtual void | setPressure (doublereal p) |
| Set the internally stored pressure (Pa) at constant temperature and composition. More... | |
| virtual void | setState_TP (doublereal T, doublereal pres) |
| Set the temperature and pressure at the same time. More... | |
| virtual doublereal | pressure () const |
| Returns the current pressure of the phase. More... | |
| virtual void | updateStandardStateThermo () const |
| Updates the standard state thermodynamic functions at the current T and P of the solution. More... | |
| void | installPDSS (size_t k, std::unique_ptr< PDSS > &&pdss) |
| Install a PDSS object for species k More... | |
| PDSS * | providePDSS (size_t k) |
| const PDSS * | providePDSS (size_t k) const |
| virtual bool | addSpecies (shared_ptr< Species > spec) |
| Add a Species to this Phase. More... | |
| virtual void | getEnthalpy_RT_ref (doublereal *hrt) const |
| virtual void | getGibbs_RT_ref (doublereal *grt) const |
| Returns the vector of nondimensional Gibbs Free Energies of the reference state at the current temperature of the solution and the reference pressure for the species. More... | |
| virtual void | getGibbs_ref (doublereal *g) const |
| Returns the vector of the Gibbs function of the reference state at the current temperature of the solution and the reference pressure for the species. More... | |
| virtual void | getEntropy_R_ref (doublereal *er) const |
| Returns the vector of nondimensional entropies of the reference state at the current temperature of the solution and the reference pressure for each species. More... | |
| virtual void | getCp_R_ref (doublereal *cprt) const |
| Returns the vector of nondimensional constant pressure heat capacities of the reference state at the current temperature of the solution and reference pressure for each species. More... | |
| virtual void | getStandardVolumes_ref (doublereal *vol) const |
| Get the molar volumes of the species reference states at the current T and P_ref of the solution. More... | |
| Public Member Functions inherited from ThermoPhase | |
| ThermoPhase () | |
| Constructor. More... | |
| doublereal | RT () const |
| Return the Gas Constant multiplied by the current temperature. More... | |
| virtual doublereal | refPressure () const |
| Returns the reference pressure in Pa. More... | |
| virtual doublereal | minTemp (size_t k=npos) const |
| Minimum temperature for which the thermodynamic data for the species or phase are valid. More... | |
| doublereal | Hf298SS (const size_t k) const |
| Report the 298 K Heat of Formation of the standard state of one species (J kmol-1) More... | |
| virtual void | modifyOneHf298SS (const size_t k, const doublereal Hf298New) |
| Modify the value of the 298 K Heat of Formation of one species in the phase (J kmol-1) More... | |
| virtual void | resetHf298 (const size_t k=npos) |
| Restore the original heat of formation of one or more species. More... | |
| virtual doublereal | maxTemp (size_t k=npos) const |
| Maximum temperature for which the thermodynamic data for the species are valid. More... | |
| bool | chargeNeutralityNecessary () const |
| Returns the chargeNeutralityNecessity boolean. More... | |
| virtual doublereal | intEnergy_mole () const |
| Molar internal energy. Units: J/kmol. More... | |
| virtual doublereal | gibbs_mole () const |
| Molar Gibbs function. Units: J/kmol. More... | |
| virtual doublereal | isothermalCompressibility () const |
| Returns the isothermal compressibility. Units: 1/Pa. More... | |
| virtual doublereal | thermalExpansionCoeff () const |
| Return the volumetric thermal expansion coefficient. Units: 1/K. More... | |
| void | setElectricPotential (doublereal v) |
| Set the electric potential of this phase (V). More... | |
| doublereal | electricPotential () const |
| Returns the electric potential of this phase (V). More... | |
| virtual int | activityConvention () const |
| This method returns the convention used in specification of the activities, of which there are currently two, molar- and molality-based conventions. More... | |
| virtual void | getLnActivityCoefficients (doublereal *lnac) const |
| Get the array of non-dimensional molar-based ln activity coefficients at the current solution temperature, pressure, and solution concentration. More... | |
| void | getElectrochemPotentials (doublereal *mu) const |
| Get the species electrochemical potentials. More... | |
| virtual void | getPartialMolarIntEnergies (doublereal *ubar) const |
| Return an array of partial molar internal energies for the species in the mixture. More... | |
| virtual void | getIntEnergy_RT_ref (doublereal *urt) const |
| Returns the vector of nondimensional internal Energies of the reference state at the current temperature of the solution and the reference pressure for each species. More... | |
| doublereal | enthalpy_mass () const |
| Specific enthalpy. Units: J/kg. More... | |
| doublereal | intEnergy_mass () const |
| Specific internal energy. Units: J/kg. More... | |
| doublereal | entropy_mass () const |
| Specific entropy. Units: J/kg/K. More... | |
| doublereal | gibbs_mass () const |
| Specific Gibbs function. Units: J/kg. More... | |
| doublereal | cp_mass () const |
| Specific heat at constant pressure. Units: J/kg/K. More... | |
| doublereal | cv_mass () const |
| Specific heat at constant volume. Units: J/kg/K. More... | |
| virtual void | setState_TPX (doublereal t, doublereal p, const doublereal *x) |
| Set the temperature (K), pressure (Pa), and mole fractions. More... | |
| virtual void | setState_TPX (doublereal t, doublereal p, const compositionMap &x) |
| Set the temperature (K), pressure (Pa), and mole fractions. More... | |
| virtual void | setState_TPX (doublereal t, doublereal p, const std::string &x) |
| Set the temperature (K), pressure (Pa), and mole fractions. More... | |
| virtual void | setState_TPY (doublereal t, doublereal p, const doublereal *y) |
| Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase. More... | |
| virtual void | setState_TPY (doublereal t, doublereal p, const compositionMap &y) |
| Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase. More... | |
| virtual void | setState_TPY (doublereal t, doublereal p, const std::string &y) |
| Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase. More... | |
| virtual void | setState_PX (doublereal p, doublereal *x) |
| Set the pressure (Pa) and mole fractions. More... | |
| virtual void | setState_PY (doublereal p, doublereal *y) |
| Set the internally stored pressure (Pa) and mass fractions. More... | |
| virtual void | setState_HP (double h, double p, double tol=1e-9) |
| Set the internally stored specific enthalpy (J/kg) and pressure (Pa) of the phase. More... | |
| virtual void | setState_UV (double u, double v, double tol=1e-9) |
| Set the specific internal energy (J/kg) and specific volume (m^3/kg). More... | |
| virtual void | setState_SP (double s, double p, double tol=1e-9) |
| Set the specific entropy (J/kg/K) and pressure (Pa). More... | |
| virtual void | setState_SV (double s, double v, double tol=1e-9) |
| Set the specific entropy (J/kg/K) and specific volume (m^3/kg). More... | |
| virtual void | setState_ST (double s, double t, double tol=1e-9) |
| Set the specific entropy (J/kg/K) and temperature (K). More... | |
| virtual void | setState_TV (double t, double v, double tol=1e-9) |
| Set the temperature (K) and specific volume (m^3/kg). More... | |
| virtual void | setState_PV (double p, double v, double tol=1e-9) |
| Set the pressure (Pa) and specific volume (m^3/kg). More... | |
| virtual void | setState_UP (double u, double p, double tol=1e-9) |
| Set the specific internal energy (J/kg) and pressure (Pa). More... | |
| virtual void | setState_VH (double v, double h, double tol=1e-9) |
| Set the specific volume (m^3/kg) and the specific enthalpy (J/kg) More... | |
| virtual void | setState_TH (double t, double h, double tol=1e-9) |
| Set the temperature (K) and the specific enthalpy (J/kg) More... | |
| virtual void | setState_SH (double s, double h, double tol=1e-9) |
| Set the specific entropy (J/kg/K) and the specific enthalpy (J/kg) More... | |
| virtual void | setState_RP (doublereal rho, doublereal p) |
| Set the density (kg/m**3) and pressure (Pa) at constant composition. More... | |
| virtual void | setState_RPX (doublereal rho, doublereal p, const doublereal *x) |
| Set the density (kg/m**3), pressure (Pa) and mole fractions. More... | |
| virtual void | setState_RPX (doublereal rho, doublereal p, const compositionMap &x) |
| Set the density (kg/m**3), pressure (Pa) and mole fractions. More... | |
| virtual void | setState_RPX (doublereal rho, doublereal p, const std::string &x) |
| Set the density (kg/m**3), pressure (Pa) and mole fractions. More... | |
| virtual void | setState_RPY (doublereal rho, doublereal p, const doublereal *y) |
| Set the density (kg/m**3), pressure (Pa) and mass fractions. More... | |
| virtual void | setState_RPY (doublereal rho, doublereal p, const compositionMap &y) |
| Set the density (kg/m**3), pressure (Pa) and mass fractions. More... | |
| virtual void | setState_RPY (doublereal rho, doublereal p, const std::string &y) |
| Set the density (kg/m**3), pressure (Pa) and mass fractions. More... | |
| void | equilibrate (const std::string &XY, const std::string &solver="auto", double rtol=1e-9, int max_steps=50000, int max_iter=100, int estimate_equil=0, int log_level=0) |
| Equilibrate a ThermoPhase object. More... | |
| virtual void | setToEquilState (const doublereal *lambda_RT) |
| This method is used by the ChemEquil equilibrium solver. More... | |
| void | setElementPotentials (const vector_fp &lambda) |
| Stores the element potentials in the ThermoPhase object. More... | |
| bool | getElementPotentials (doublereal *lambda) const |
| Returns the element potentials stored in the ThermoPhase object. More... | |
| virtual bool | compatibleWithMultiPhase () const |
| Indicates whether this phase type can be used with class MultiPhase for equilibrium calculations. More... | |
| virtual doublereal | critTemperature () const |
| Critical temperature (K). More... | |
| virtual doublereal | critPressure () const |
| Critical pressure (Pa). More... | |
| virtual doublereal | critVolume () const |
| Critical volume (m3/kmol). More... | |
| virtual doublereal | critCompressibility () const |
| Critical compressibility (unitless). More... | |
| virtual doublereal | critDensity () const |
| Critical density (kg/m3). More... | |
| virtual doublereal | satTemperature (doublereal p) const |
| Return the saturation temperature given the pressure. More... | |
| virtual doublereal | satPressure (doublereal t) |
| Return the saturation pressure given the temperature. More... | |
| virtual doublereal | vaporFraction () const |
| Return the fraction of vapor at the current conditions. More... | |
| virtual void | setState_Tsat (doublereal t, doublereal x) |
| Set the state to a saturated system at a particular temperature. More... | |
| virtual void | setState_Psat (doublereal p, doublereal x) |
| Set the state to a saturated system at a particular pressure. More... | |
| virtual void | modifySpecies (size_t k, shared_ptr< Species > spec) |
| Modify the thermodynamic data associated with a species. More... | |
| void | saveSpeciesData (const size_t k, const XML_Node *const data) |
| Store a reference pointer to the XML tree containing the species data for this phase. More... | |
| const std::vector< const XML_Node * > & | speciesData () const |
| Return a pointer to the vector of XML nodes containing the species data for this phase. More... | |
| virtual MultiSpeciesThermo & | speciesThermo (int k=-1) |
| Return a changeable reference to the calculation manager for species reference-state thermodynamic properties. More... | |
| virtual void | initThermoFile (const std::string &inputFile, const std::string &id) |
| virtual void | setParameters (int n, doublereal *const c) |
| Set the equation of state parameters. More... | |
| virtual void | getParameters (int &n, doublereal *const c) const |
| Get the equation of state parameters in a vector. More... | |
| virtual void | setParametersFromXML (const XML_Node &eosdata) |
| Set equation of state parameter values from XML entries. More... | |
| virtual void | setStateFromXML (const XML_Node &state) |
| Set the initial state of the phase to the conditions specified in the state XML element. More... | |
| virtual void | getdlnActCoeffdlnN_numderiv (const size_t ld, doublereal *const dlnActCoeffdlnN) |
| virtual std::string | report (bool show_thermo=true, doublereal threshold=-1e-14) const |
| returns a summary of the state of the phase as a string More... | |
| virtual void | reportCSV (std::ofstream &csvFile) const |
| returns a summary of the state of the phase to a comma separated file. More... | |
| Public Member Functions inherited from Phase | |
| Phase () | |
| Default constructor. More... | |
| Phase (const Phase &)=delete | |
| Phase & | operator= (const Phase &)=delete |
| XML_Node & | xml () const |
| Returns a const reference to the XML_Node that describes the phase. More... | |
| void | setXMLdata (XML_Node &xmlPhase) |
| Stores the XML tree information for the current phase. More... | |
| void | saveState (vector_fp &state) const |
| Save the current internal state of the phase. More... | |
| void | saveState (size_t lenstate, doublereal *state) const |
| Write to array 'state' the current internal state. More... | |
| void | restoreState (const vector_fp &state) |
| Restore a state saved on a previous call to saveState. More... | |
| void | restoreState (size_t lenstate, const doublereal *state) |
| Restore the state of the phase from a previously saved state vector. More... | |
| doublereal | molecularWeight (size_t k) const |
Molecular weight of species k. More... | |
| void | getMolecularWeights (vector_fp &weights) const |
| Copy the vector of molecular weights into vector weights. More... | |
| void | getMolecularWeights (doublereal *weights) const |
| Copy the vector of molecular weights into array weights. More... | |
| const vector_fp & | molecularWeights () const |
| Return a const reference to the internal vector of molecular weights. More... | |
| virtual double | size (size_t k) const |
| doublereal | charge (size_t k) const |
| Dimensionless electrical charge of a single molecule of species k The charge is normalized by the the magnitude of the electron charge. More... | |
| doublereal | chargeDensity () const |
| Charge density [C/m^3]. More... | |
| size_t | nDim () const |
| Returns the number of spatial dimensions (1, 2, or 3) More... | |
| void | setNDim (size_t ndim) |
| Set the number of spatial dimensions (1, 2, or 3). More... | |
| virtual bool | ready () const |
| Returns a bool indicating whether the object is ready for use. More... | |
| int | stateMFNumber () const |
| Return the State Mole Fraction Number. More... | |
| std::string | id () const |
| Return the string id for the phase. More... | |
| void | setID (const std::string &id) |
| Set the string id for the phase. More... | |
| std::string | name () const |
| Return the name of the phase. More... | |
| void | setName (const std::string &nm) |
| Sets the string name for the phase. More... | |
| std::string | elementName (size_t m) const |
| Name of the element with index m. More... | |
| size_t | elementIndex (const std::string &name) const |
| Return the index of element named 'name'. More... | |
| const std::vector< std::string > & | elementNames () const |
| Return a read-only reference to the vector of element names. More... | |
| doublereal | atomicWeight (size_t m) const |
| Atomic weight of element m. More... | |
| doublereal | entropyElement298 (size_t m) const |
| Entropy of the element in its standard state at 298 K and 1 bar. More... | |
| int | atomicNumber (size_t m) const |
| Atomic number of element m. More... | |
| int | elementType (size_t m) const |
| Return the element constraint type Possible types include: More... | |
| int | changeElementType (int m, int elem_type) |
| Change the element type of the mth constraint Reassigns an element type. More... | |
| const vector_fp & | atomicWeights () const |
| Return a read-only reference to the vector of atomic weights. More... | |
| size_t | nElements () const |
| Number of elements. More... | |
| void | checkElementIndex (size_t m) const |
| Check that the specified element index is in range. More... | |
| void | checkElementArraySize (size_t mm) const |
| Check that an array size is at least nElements(). More... | |
| doublereal | nAtoms (size_t k, size_t m) const |
Number of atoms of element m in species k. More... | |
| void | getAtoms (size_t k, double *atomArray) const |
| Get a vector containing the atomic composition of species k. More... | |
| size_t | speciesIndex (const std::string &name) const |
| Returns the index of a species named 'name' within the Phase object. More... | |
| std::string | speciesName (size_t k) const |
| Name of the species with index k. More... | |
| std::string | speciesSPName (int k) const |
| Returns the expanded species name of a species, including the phase name This is guaranteed to be unique within a Cantera problem. More... | |
| const std::vector< std::string > & | speciesNames () const |
| Return a const reference to the vector of species names. More... | |
| size_t | nSpecies () const |
| Returns the number of species in the phase. More... | |
| void | checkSpeciesIndex (size_t k) const |
| Check that the specified species index is in range. More... | |
| void | checkSpeciesArraySize (size_t kk) const |
| Check that an array size is at least nSpecies(). More... | |
| void | setMoleFractionsByName (const compositionMap &xMap) |
| Set the species mole fractions by name. More... | |
| void | setMoleFractionsByName (const std::string &x) |
| Set the mole fractions of a group of species by name. More... | |
| void | setMassFractionsByName (const compositionMap &yMap) |
| Set the species mass fractions by name. More... | |
| void | setMassFractionsByName (const std::string &x) |
| Set the species mass fractions by name. More... | |
| void | setState_TRX (doublereal t, doublereal dens, const doublereal *x) |
| Set the internally stored temperature (K), density, and mole fractions. More... | |
| void | setState_TRX (doublereal t, doublereal dens, const compositionMap &x) |
| Set the internally stored temperature (K), density, and mole fractions. More... | |
| void | setState_TRY (doublereal t, doublereal dens, const doublereal *y) |
| Set the internally stored temperature (K), density, and mass fractions. More... | |
| void | setState_TRY (doublereal t, doublereal dens, const compositionMap &y) |
| Set the internally stored temperature (K), density, and mass fractions. More... | |
| void | setState_TNX (doublereal t, doublereal n, const doublereal *x) |
| Set the internally stored temperature (K), molar density (kmol/m^3), and mole fractions. More... | |
| void | setState_TR (doublereal t, doublereal rho) |
| Set the internally stored temperature (K) and density (kg/m^3) More... | |
| void | setState_TX (doublereal t, doublereal *x) |
| Set the internally stored temperature (K) and mole fractions. More... | |
| void | setState_TY (doublereal t, doublereal *y) |
| Set the internally stored temperature (K) and mass fractions. More... | |
| void | setState_RX (doublereal rho, doublereal *x) |
| Set the density (kg/m^3) and mole fractions. More... | |
| void | setState_RY (doublereal rho, doublereal *y) |
| Set the density (kg/m^3) and mass fractions. More... | |
| compositionMap | getMoleFractionsByName (double threshold=0.0) const |
| Get the mole fractions by name. More... | |
| doublereal | moleFraction (size_t k) const |
| Return the mole fraction of a single species. More... | |
| doublereal | moleFraction (const std::string &name) const |
| Return the mole fraction of a single species. More... | |
| compositionMap | getMassFractionsByName (double threshold=0.0) const |
| Get the mass fractions by name. More... | |
| doublereal | massFraction (size_t k) const |
| Return the mass fraction of a single species. More... | |
| doublereal | massFraction (const std::string &name) const |
| Return the mass fraction of a single species. More... | |
| void | getMoleFractions (doublereal *const x) const |
| Get the species mole fraction vector. More... | |
| virtual void | setMoleFractions (const doublereal *const x) |
| Set the mole fractions to the specified values. More... | |
| virtual void | setMoleFractions_NoNorm (const doublereal *const x) |
| Set the mole fractions to the specified values without normalizing. More... | |
| void | getMassFractions (doublereal *const y) const |
| Get the species mass fractions. More... | |
| const doublereal * | massFractions () const |
| Return a const pointer to the mass fraction array. More... | |
| virtual void | setMassFractions (const doublereal *const y) |
| Set the mass fractions to the specified values and normalize them. More... | |
| virtual void | setMassFractions_NoNorm (const doublereal *const y) |
| Set the mass fractions to the specified values without normalizing. More... | |
| void | getConcentrations (doublereal *const c) const |
| Get the species concentrations (kmol/m^3). More... | |
| doublereal | concentration (const size_t k) const |
| Concentration of species k. More... | |
| virtual void | setConcentrations (const doublereal *const conc) |
| Set the concentrations to the specified values within the phase. More... | |
| virtual void | setConcentrationsNoNorm (const double *const conc) |
| Set the concentrations without ignoring negative concentrations. More... | |
| doublereal | elementalMassFraction (const size_t m) const |
| Elemental mass fraction of element m. More... | |
| doublereal | elementalMoleFraction (const size_t m) const |
| Elemental mole fraction of element m. More... | |
| const doublereal * | moleFractdivMMW () const |
| Returns a const pointer to the start of the moleFraction/MW array. More... | |
| doublereal | temperature () const |
| Temperature (K). More... | |
| virtual doublereal | density () const |
| Density (kg/m^3). More... | |
| doublereal | molarDensity () const |
| Molar density (kmol/m^3). More... | |
| doublereal | molarVolume () const |
| Molar volume (m^3/kmol). More... | |
| virtual void | setDensity (const doublereal density_) |
| Set the internally stored density (kg/m^3) of the phase. More... | |
| virtual void | setMolarDensity (const doublereal molarDensity) |
| Set the internally stored molar density (kmol/m^3) of the phase. More... | |
| doublereal | mean_X (const doublereal *const Q) const |
| Evaluate the mole-fraction-weighted mean of an array Q. More... | |
| doublereal | mean_X (const vector_fp &Q) const |
| Evaluate the mole-fraction-weighted mean of an array Q. More... | |
| doublereal | meanMolecularWeight () const |
| The mean molecular weight. Units: (kg/kmol) More... | |
| doublereal | sum_xlogx () const |
| Evaluate \( \sum_k X_k \log X_k \). More... | |
| size_t | addElement (const std::string &symbol, doublereal weight=-12345.0, int atomicNumber=0, doublereal entropy298=ENTROPY298_UNKNOWN, int elem_type=CT_ELEM_TYPE_ABSPOS) |
| Add an element. More... | |
| shared_ptr< Species > | species (const std::string &name) const |
| Return the Species object for the named species. More... | |
| shared_ptr< Species > | species (size_t k) const |
| Return the Species object for species whose index is k. More... | |
| void | ignoreUndefinedElements () |
| Set behavior when adding a species containing undefined elements to just skip the species. More... | |
| void | addUndefinedElements () |
| Set behavior when adding a species containing undefined elements to add those elements to the phase. More... | |
| void | throwUndefinedElements () |
| Set the behavior when adding a species containing undefined elements to throw an exception. More... | |
Protected Attributes | |
| size_t | numBinaryInteractions_ |
| number of binary interaction expressions More... | |
| vector_fp | m_HE_b_ij |
| Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_HE_c_ij |
| Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_HE_d_ij |
| Enthalpy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_SE_b_ij |
| Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_SE_c_ij |
| Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_SE_d_ij |
| Entropy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_VHE_b_ij |
| Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_VHE_c_ij |
| Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_VHE_d_ij |
| Enthalpy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_VSE_b_ij |
| Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_VSE_c_ij |
| Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| vector_fp | m_VSE_d_ij |
| Entropy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression. More... | |
| std::vector< size_t > | m_pSpecies_A_ij |
| vector of species indices representing species A in the interaction More... | |
| std::vector< size_t > | m_pSpecies_B_ij |
| vector of species indices representing species B in the interaction More... | |
| int | formMargules_ |
| form of the Margules interaction expression More... | |
| int | formTempModel_ |
| form of the temperature dependence of the Margules interaction expression More... | |
| Protected Attributes inherited from GibbsExcessVPSSTP | |
| vector_fp | moleFractions_ |
| Storage for the current values of the mole fractions of the species. More... | |
| vector_fp | lnActCoeff_Scaled_ |
| Storage for the current values of the activity coefficients of the species. More... | |
| vector_fp | dlnActCoeffdT_Scaled_ |
| Storage for the current derivative values of the gradients with respect to temperature of the log of the activity coefficients of the species. More... | |
| vector_fp | d2lnActCoeffdT2_Scaled_ |
| Storage for the current derivative values of the gradients with respect to temperature of the log of the activity coefficients of the species. More... | |
| vector_fp | dlnActCoeffdlnN_diag_ |
| Storage for the current derivative values of the gradients with respect to logarithm of the mole fraction of the log of the activity coefficients of the species. More... | |
| vector_fp | dlnActCoeffdlnX_diag_ |
| Storage for the current derivative values of the gradients with respect to logarithm of the mole fraction of the log of the activity coefficients of the species. More... | |
| Array2D | dlnActCoeffdlnN_ |
| Storage for the current derivative values of the gradients with respect to logarithm of the species mole number of the log of the activity coefficients of the species. More... | |
| Protected Attributes inherited from VPStandardStateTP | |
| doublereal | m_Pcurrent |
| Current value of the pressure - state variable. More... | |
| doublereal | m_Tlast_ss |
| The last temperature at which the standard statethermodynamic properties were calculated at. More... | |
| doublereal | m_Plast_ss |
| The last pressure at which the Standard State thermodynamic properties were calculated at. More... | |
| std::vector< std::unique_ptr< PDSS > > | m_PDSS_storage |
| Storage for the PDSS objects for the species. More... | |
| vector_fp | m_h0_RT |
| Vector containing the species reference enthalpies at T = m_tlast and P = p_ref. More... | |
| vector_fp | m_cp0_R |
| Vector containing the species reference constant pressure heat capacities at T = m_tlast and P = p_ref. More... | |
| vector_fp | m_g0_RT |
| Vector containing the species reference Gibbs functions at T = m_tlast and P = p_ref. More... | |
| vector_fp | m_s0_R |
| Vector containing the species reference entropies at T = m_tlast and P = p_ref. More... | |
| vector_fp | m_V0 |
| Vector containing the species reference molar volumes. More... | |
| vector_fp | m_hss_RT |
| Vector containing the species Standard State enthalpies at T = m_tlast and P = m_plast. More... | |
| vector_fp | m_cpss_R |
| Vector containing the species Standard State constant pressure heat capacities at T = m_tlast and P = m_plast. More... | |
| vector_fp | m_gss_RT |
| Vector containing the species Standard State Gibbs functions at T = m_tlast and P = m_plast. More... | |
| vector_fp | m_sss_R |
| Vector containing the species Standard State entropies at T = m_tlast and P = m_plast. More... | |
| vector_fp | m_Vss |
| Vector containing the species standard state volumes at T = m_tlast and P = m_plast. More... | |
| Protected Attributes inherited from ThermoPhase | |
| MultiSpeciesThermo | m_spthermo |
| Pointer to the calculation manager for species reference-state thermodynamic properties. More... | |
| std::vector< const XML_Node * > | m_speciesData |
| Vector of pointers to the species databases. More... | |
| doublereal | m_phi |
| Stored value of the electric potential for this phase. Units are Volts. More... | |
| vector_fp | m_lambdaRRT |
| Vector of element potentials. More... | |
| bool | m_hasElementPotentials |
| Boolean indicating whether there is a valid set of saved element potentials for this phase. More... | |
| bool | m_chargeNeutralityNecessary |
| Boolean indicating whether a charge neutrality condition is a necessity. More... | |
| int | m_ssConvention |
| Contains the standard state convention. More... | |
| doublereal | m_tlast |
| last value of the temperature processed by reference state More... | |
| Protected Attributes inherited from Phase | |
| ValueCache | m_cache |
| Cached for saved calculations within each ThermoPhase. More... | |
| size_t | m_kk |
| Number of species in the phase. More... | |
| size_t | m_ndim |
| Dimensionality of the phase. More... | |
| vector_fp | m_speciesComp |
| Atomic composition of the species. More... | |
| vector_fp | m_speciesCharge |
| Vector of species charges. length m_kk. More... | |
| std::map< std::string, shared_ptr< Species > > | m_species |
| UndefElement::behavior | m_undefinedElementBehavior |
| Flag determining behavior when adding species with an undefined element. More... | |
Private Member Functions | |
| void | readXMLBinarySpecies (XML_Node &xmlBinarySpecies) |
| Process an XML node called "binaryNeutralSpeciesParameters". More... | |
| void | resizeNumInteractions (const size_t num) |
| Resize internal arrays within the object that depend upon the number of binary Margules interaction terms. More... | |
| void | initLengths () |
| Initialize lengths of local variables after all species have been identified. More... | |
| void | s_update_lnActCoeff () const |
| Update the activity coefficients. More... | |
| void | s_update_dlnActCoeff_dT () const |
| Update the derivative of the log of the activity coefficients wrt T. More... | |
| void | s_update_dlnActCoeff_dlnX_diag () const |
| Update the derivative of the log of the activity coefficients wrt log(mole fraction) More... | |
| void | s_update_dlnActCoeff_dlnN_diag () const |
| Update the derivative of the log of the activity coefficients wrt log(moles) - diagonal only. More... | |
| void | s_update_dlnActCoeff_dlnN () const |
| Update the derivative of the log of the activity coefficients wrt log(moles_m) More... | |
Additional Inherited Members | |
| Protected Member Functions inherited from GibbsExcessVPSSTP | |
| void | calcDensity () |
| Calculate the density of the mixture using the partial molar volumes and mole fractions as input. More... | |
| virtual void | compositionChanged () |
| Apply changes to the state which are needed after the composition changes. More... | |
| double | checkMFSum (const doublereal *const x) const |
| utility routine to check mole fraction sum More... | |
| Protected Member Functions inherited from VPStandardStateTP | |
| virtual void | _updateStandardStateThermo () const |
| Updates the standard state thermodynamic functions at the current T and P of the solution. More... | |
| virtual void | invalidateCache () |
| Invalidate any cached values which are normally updated only when a change in state is detected. More... | |
| const vector_fp & | Gibbs_RT_ref () const |
| Protected Member Functions inherited from ThermoPhase | |
| virtual void | getCsvReportData (std::vector< std::string > &names, std::vector< vector_fp > &data) const |
Fills names and data with the column names and species thermo properties to be included in the output of the reportCSV method. More... | |
| Protected Member Functions inherited from Phase | |
| void | setMolecularWeight (const int k, const double mw) |
| Set the molecular weight of a single species to a given value. More... | |
Detailed Description
PhaseCombo_Interaction is a derived class of GibbsExcessVPSSTP that employs the Margules approximation for the excess Gibbs free energy while eliminating the entropy of mixing term.
- Attention
- This class currently does not have any test cases or examples. Its implementation may be incomplete, and future changes to Cantera may unexpectedly cause this class to stop working. If you use this class, please consider contributing examples or test cases. In the absence of new tests or examples, this class may be deprecated and removed in a future version of Cantera. See https://github.com/Cantera/cantera/issues/267 for additional information.
- Deprecated:
- To be removed after Cantera 2.4
PhaseCombo_Interaction derives from class GibbsExcessVPSSTP which is derived from VPStandardStateTP, and overloads the virtual methods defined there with ones that use expressions appropriate for the Margules Excess Gibbs free energy approximation. The reader should refer to the MargulesVPSSTP class for information on that class. This class in addition adds a term to the activity coefficient that eliminates the ideal solution mixing term within the chemical potential. This is a very radical thing to do, but it is supported by experimental evidence under some conditions.
The independent unknowns are pressure, temperature, and mass fraction.
This class is introduced to represent specific conditions observed in thermal batteries. HOwever, it may be physically motivated to represent conditions where there may be a mixture of compounds that are not "mixed" at the molecular level. Therefore, there is no mixing term.
The lack of a mixing term has profound effects. First, the mole fraction of a species can now be identically zero due to thermodynamic considerations. The phase behaves more like a series of phases. That's why we named it PhaseCombo.
Specification of Species Standard State Properties
All species are defined to have standard states that depend upon both the temperature and the pressure. The Margules approximation assumes symmetric standard states, where all of the standard state assume that the species are in pure component states at the temperature and pressure of the solution. I don't think it prevents, however, some species from being dilute in the solution.
Specification of Solution Thermodynamic Properties
The molar excess Gibbs free energy is given by the following formula which is a sum over interactions i. Each of the interactions are binary interactions involving two of the species in the phase, denoted, Ai and Bi. This is the generalization of the Margules formulation for a phase that has more than 2 species. The second term in the excess Gibbs free energy is a negation of the ideal solution's mixing term.
\[ G^E = \sum_i \left( H_{Ei} - T S_{Ei} \right) - \sum_i \left( n_i R T \ln{X_i} \right) \]
\[ H^E_i = n X_{Ai} X_{Bi} \left( h_{o,i} + h_{1,i} X_{Bi} \right) \]
\[ S^E_i = n X_{Ai} X_{Bi} \left( s_{o,i} + s_{1,i} X_{Bi} \right) \]
where n is the total moles in the solution. The activity of a species defined in the phase is given by an excess Gibbs free energy formulation.
\[ a_k = \gamma_k X_k \]
where
\[ R T \ln( \gamma_k )= \frac{d(n G^E)}{d(n_k)}\Bigg|_{n_i} \]
Taking the derivatives results in the following expression
\[ R T \ln( \gamma_k )= \sum_i \left( \left( \delta_{Ai,k} X_{Bi} + \delta_{Bi,k} X_{Ai} - X_{Ai} X_{Bi} \right) \left( g^E_{o,i} + g^E_{1,i} X_{Bi} \right) + \left( \delta_{Bi,k} - X_{Bi} \right) X_{Ai} X_{Bi} g^E_{1,i} \right) - RT \ln{X_k} \]
where \( g^E_{o,i} = h_{o,i} - T s_{o,i} \) and \( g^E_{1,i} = h_{1,i} - T s_{1,i} \) and where \( X_k \) is the mole fraction of species k.
This object inherits from the class VPStandardStateTP. Therefore, the specification and calculation of all standard state and reference state values are handled at that level. Various functional forms for the standard state are permissible. The chemical potential for species k is equal to
\[ \mu_k(T,P) = \mu^o_k(T, P) + R T \ln(\gamma_k X_k) \]
The partial molar entropy for species k is given by the following relation,
\[ \tilde{s}_k(T,P) = s^o_k(T,P) - R \ln( \gamma_k X_k ) - R T \frac{d \ln(\gamma_k) }{dT} \]
The partial molar enthalpy for species k is given by
\[ \tilde{h}_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} \]
The partial molar volume for species k is
\[ \tilde V_k(T,P) = V^o_k(T,P) + R T \frac{d \ln(\gamma_k) }{dP} \]
The partial molar Heat Capacity for species k is
\[ \tilde{C}_{p,k}(T,P) = C^o_{p,k}(T,P) - 2 R T \frac{d \ln( \gamma_k )}{dT} - R T^2 \frac{d^2 \ln(\gamma_k) }{{dT}^2} \]
Application within Kinetics Managers
\( C^a_k\) are defined such that \( a_k = C^a_k / C^s_k, \) where \( C^s_k \) is a standard concentration defined below and \( a_k \) are activities used in the thermodynamic functions. These activity (or generalized) concentrations are used by kinetics manager classes to compute the forward and reverse rates of elementary reactions. The activity concentration, \( C^a_k \),is given by the following expression.
\[ C^a_k = C^s_k X_k = \frac{P}{R T} X_k \]
The standard concentration for species k is independent of k and equal to
\[ C^s_k = C^s = \frac{P}{R T} \]
For example, a bulk-phase binary gas reaction between species j and k, producing a new gas species l would have the following equation for its rate of progress variable, \( R^1 \), which has units of kmol m-3 s-1.
\[ R^1 = k^1 C_j^a C_k^a = k^1 (C^s a_j) (C^s a_k) \]
where
\[ C_j^a = C^s a_j \mbox{\quad and \quad} C_k^a = C^s a_k \]
\( C_j^a \) is the activity concentration of species j, and \( C_k^a \) is the activity concentration of species k. \( C^s \) is the standard concentration. \( a_j \) is the activity of species j which is equal to the mole fraction of j.
The reverse rate constant can then be obtained from the law of microscopic reversibility and the equilibrium expression for the system.
\[ \frac{a_j a_k}{ a_l} = K_a^{o,1} = \exp(\frac{\mu^o_l - \mu^o_j - \mu^o_k}{R T} ) \]
\( K_a^{o,1} \) is the dimensionless form of the equilibrium constant, associated with the pressure dependent standard states \( \mu^o_l(T,P) \) and their associated activities, \( a_l \), repeated here:
\[ \mu_l(T,P) = \mu^o_l(T, P) + R T \log(a_l) \]
We can switch over to expressing the equilibrium constant in terms of the reference state chemical potentials
\[ K_a^{o,1} = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{P} \]
The concentration equilibrium constant, \( K_c \), may be obtained by changing over to activity concentrations. When this is done:
\[ \frac{C^a_j C^a_k}{ C^a_l} = C^o K_a^{o,1} = K_c^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{RT} \]
Kinetics managers will calculate the concentration equilibrium constant, \( K_c \), using the second and third part of the above expression as a definition for the concentration equilibrium constant.
For completeness, the pressure equilibrium constant may be obtained as well
\[ \frac{P_j P_k}{ P_l P_{ref}} = K_p^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) \]
\( K_p \) is the simplest form of the equilibrium constant for ideal gases. However, it isn't necessarily the simplest form of the equilibrium constant for other types of phases; \( K_c \) is used instead because it is completely general.
The reverse rate of progress may be written down as
\[ R^{-1} = k^{-1} C_l^a = k^{-1} (C^o a_l) \]
where we can use the concept of microscopic reversibility to write the reverse rate constant in terms of the forward reate constant and the concentration equilibrium constant, \( K_c \).
\[ k^{-1} = k^1 K^1_c \]
\(k^{-1} \) has units of s-1.
Instantiation of the Class
The constructor for this phase is located in the default ThermoFactory for Cantera. A new PhaseCombo_Interaction object may be created by the following code snippet:
or by the following code
or by the following constructor:
XML Example
An example of an XML Element named phase setting up a PhaseCombo_Interaction object named LiFeS_X is given below.
The model attribute "PhaseCombo_Interaction" of the thermo XML element identifies the phase as being of the type handled by the PhaseCombo_Interaction object.
Definition at line 312 of file PhaseCombo_Interaction.h.
Constructor & Destructor Documentation
◆ PhaseCombo_Interaction() [1/3]
Constructor.
Definition at line 17 of file PhaseCombo_Interaction.cpp.
References Cantera::warn_deprecated().
◆ PhaseCombo_Interaction() [2/3]
| PhaseCombo_Interaction | ( | const std::string & | inputFile, |
| const std::string & | id = "" |
||
| ) |
Construct and initialize a PhaseCombo_Interaction ThermoPhase object directly from an XML input file.
- Parameters
-
inputFile Name of the input file containing the phase XML data to set up the object id ID of the phase in the input file. Defaults to the empty string.
Definition at line 25 of file PhaseCombo_Interaction.cpp.
References ThermoPhase::initThermoFile(), and Cantera::warn_deprecated().
◆ PhaseCombo_Interaction() [3/3]
| PhaseCombo_Interaction | ( | XML_Node & | phaseRef, |
| const std::string & | id = "" |
||
| ) |
Construct and initialize a PhaseCombo_Interaction ThermoPhase object directly from an XML database.
- Parameters
-
phaseRef XML phase node containing the description of the phase id id attribute containing the name of the phase. (default is the empty string)
Definition at line 35 of file PhaseCombo_Interaction.cpp.
References Cantera::importPhase(), and Cantera::warn_deprecated().
Member Function Documentation
◆ type()
|
inlinevirtual |
String indicating the thermodynamic model implemented.
Usually corresponds to the name of the derived class, less any suffixes such as "Phase", TP", "VPSS", etc.
Reimplemented from ThermoPhase.
Definition at line 340 of file PhaseCombo_Interaction.h.
◆ enthalpy_mole()
|
virtual |
Molar enthalpy. Units: J/kmol.
Reimplemented from ThermoPhase.
Definition at line 74 of file PhaseCombo_Interaction.cpp.
References PhaseCombo_Interaction::getPartialMolarEnthalpies(), Phase::m_kk, and GibbsExcessVPSSTP::moleFractions_.
◆ entropy_mole()
|
virtual |
Molar entropy. Units: J/kmol/K.
Reimplemented from ThermoPhase.
Definition at line 85 of file PhaseCombo_Interaction.cpp.
References PhaseCombo_Interaction::getPartialMolarEntropies(), Phase::m_kk, and GibbsExcessVPSSTP::moleFractions_.
◆ cp_mole()
|
virtual |
Molar heat capacity at constant pressure. Units: J/kmol/K.
Reimplemented from ThermoPhase.
Definition at line 96 of file PhaseCombo_Interaction.cpp.
References PhaseCombo_Interaction::getPartialMolarCp(), Phase::m_kk, and GibbsExcessVPSSTP::moleFractions_.
Referenced by PhaseCombo_Interaction::cv_mole().
◆ cv_mole()
|
virtual |
Molar heat capacity at constant volume. Units: J/kmol/K.
Reimplemented from ThermoPhase.
Definition at line 107 of file PhaseCombo_Interaction.cpp.
References PhaseCombo_Interaction::cp_mole(), and Cantera::GasConstant.
◆ getActivityCoefficients()
|
virtual |
Get the array of non-dimensional molar-based activity coefficients at the current solution temperature, pressure, and solution concentration.
- Parameters
-
ac Output vector of activity coefficients. Length: m_kk.
Reimplemented from GibbsExcessVPSSTP.
Definition at line 47 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::lnActCoeff_Scaled_, Phase::m_kk, and PhaseCombo_Interaction::s_update_lnActCoeff().
◆ getChemPotentials()
|
virtual |
Get the species chemical potentials. Units: J/kmol.
This function returns a vector of chemical potentials of the species in solution at the current temperature, pressure and mole fraction of the solution.
- Parameters
-
mu Output vector of species chemical potentials. Length: m_kk. Units: J/kmol
Reimplemented from ThermoPhase.
Definition at line 60 of file PhaseCombo_Interaction.cpp.
References VPStandardStateTP::getStandardChemPotentials(), GibbsExcessVPSSTP::lnActCoeff_Scaled_, Phase::m_kk, GibbsExcessVPSSTP::moleFractions_, ThermoPhase::RT(), PhaseCombo_Interaction::s_update_lnActCoeff(), and Cantera::SmallNumber.
◆ getPartialMolarEnthalpies()
|
virtual |
Returns an array of partial molar enthalpies for the species in the mixture.
Units (J/kmol)
For this phase, the partial molar enthalpies are equal to the standard state enthalpies modified by the derivative of the molality-based activity coefficient wrt temperature
\[ \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} \]
- Parameters
-
hbar Vector of returned partial molar enthalpies (length m_kk, units = J/kmol)
Reimplemented from ThermoPhase.
Definition at line 112 of file PhaseCombo_Interaction.cpp.
References VPStandardStateTP::getEnthalpy_RT().
Referenced by PhaseCombo_Interaction::enthalpy_mole().
◆ getPartialMolarEntropies()
|
virtual |
Returns an array of partial molar entropies for the species in the mixture.
Units (J/kmol)
For this phase, the partial molar enthalpies are equal to the standard state enthalpies modified by the derivative of the activity coefficient wrt temperature
\[ \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} - R \ln( \gamma_k X_k) - R T \frac{d \ln(\gamma_k) }{dT} \]
- Parameters
-
sbar Vector of returned partial molar entropies (length m_kk, units = J/kmol/K)
Reimplemented from ThermoPhase.
Definition at line 152 of file PhaseCombo_Interaction.cpp.
References VPStandardStateTP::getEntropy_R().
Referenced by PhaseCombo_Interaction::entropy_mole().
◆ getPartialMolarCp()
|
virtual |
Returns an array of partial molar entropies for the species in the mixture.
Units (J/kmol)
For this phase, the partial molar enthalpies are equal to the standard state enthalpies modified by the derivative of the activity coefficient wrt temperature
\[ ??????????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} - R \ln( \gamma_k X_k) - R T \frac{d \ln(\gamma_k) }{dT} ??????????????? \]
- Parameters
-
cpbar Vector of returned partial molar heat capacities (length m_kk, units = J/kmol/K)
Reimplemented from ThermoPhase.
Definition at line 131 of file PhaseCombo_Interaction.cpp.
References VPStandardStateTP::getCp_R().
Referenced by PhaseCombo_Interaction::cp_mole().
◆ getPartialMolarVolumes()
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virtual |
Return an array of partial molar volumes for the species in the mixture.
Units: m^3/kmol.
Frequently, for this class of thermodynamics representations, the excess Volume due to mixing is zero. Here, we set it as a default. It may be overridden in derived classes.
- Parameters
-
vbar Output vector of species partial molar volumes. Length = m_kk. units are m^3/kmol.
Reimplemented from GibbsExcessVPSSTP.
Definition at line 174 of file PhaseCombo_Interaction.cpp.
◆ getd2lnActCoeffdT2()
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virtual |
Get the array of temperature second derivatives of the log activity coefficients.
units = 1/Kelvin
- Parameters
-
d2lnActCoeffdT2 Output vector of temperature 2nd derivatives of the log Activity Coefficients. length = m_kk
Definition at line 324 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::d2lnActCoeffdT2_Scaled_, Phase::m_kk, and PhaseCombo_Interaction::s_update_dlnActCoeff_dT().
◆ getdlnActCoeffdT()
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virtual |
Get the array of temperature derivatives of the log activity coefficients.
This function is virtual, and first appears in GibbsExcessVPSSTP.
units = 1/Kelvin
- Parameters
-
dlnActCoeffdT Output vector of temperature derivatives of the log Activity Coefficients. length = m_kk
Reimplemented from GibbsExcessVPSSTP.
Definition at line 316 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::dlnActCoeffdT_Scaled_, Phase::m_kk, and PhaseCombo_Interaction::s_update_dlnActCoeff_dT().
◆ initThermo()
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virtual |
The following methods are used in the process of constructing the phase and setting its parameters from a specification in an input file. They are not normally used in application programs. To see how they are used, see importPhase().
Reimplemented from VPStandardStateTP.
Definition at line 203 of file PhaseCombo_Interaction.cpp.
References PhaseCombo_Interaction::initLengths(), and VPStandardStateTP::initThermo().
◆ initThermoXML()
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virtual |
Import and initialize a ThermoPhase object using an XML tree.
Here we read extra information about the XML description of a phase. Regular information about elements and species and their reference state thermodynamic information have already been read at this point. For example, we do not need to call this function for ideal gas equations of state. This function is called from importPhase() after the elements and the species are initialized with default ideal solution level data.
The default implementation in ThermoPhase calls the virtual function initThermo() and then sets the "state" of the phase by looking for an XML element named "state", and then interpreting its contents by calling the virtual function setStateFromXML().
- Parameters
-
phaseNode This object must be the phase node of a complete XML tree description of the phase, including all of the species data. In other words while "phase" must point to an XML phase object, it must have sibling nodes "speciesData" that describe the species in the phase. id ID of the phase. If nonnull, a check is done to see if phaseNode is pointing to the phase with the correct id.
Reimplemented from ThermoPhase.
Definition at line 214 of file PhaseCombo_Interaction.cpp.
References Cantera::caseInsensitiveEquals(), XML_Node::child(), XML_Node::hasChild(), Phase::id(), XML_Node::id(), ThermoPhase::initThermoXML(), XML_Node::name(), XML_Node::nChildren(), PhaseCombo_Interaction::readXMLBinarySpecies(), and Phase::size().
◆ getdlnActCoeffds()
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virtual |
Get the change in activity coefficients wrt changes in state (temp, mole fraction, etc) along a line in parameter space or along a line in physical space.
- Parameters
-
dTds Input of temperature change along the path dXds Input vector of changes in mole fraction along the path. length = m_kk Along the path length it must be the case that the mole fractions sum to one. dlnActCoeffds Output vector of the directional derivatives of the log Activity Coefficients along the path. length = m_kk units are 1/units(s). if s is a physical coordinate then the units are 1/m.
Reimplemented from ThermoPhase.
Definition at line 332 of file PhaseCombo_Interaction.cpp.
◆ getdlnActCoeffdlnX_diag()
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virtual |
Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only.
For ideal mixtures (unity activity coefficients), this can return zero. Implementations should take the derivative of the logarithm of the activity coefficient with respect to the logarithm of the mole fraction variable that represents the standard state. This quantity is to be used in conjunction with derivatives of that mole fraction variable when the derivative of the chemical potential is taken.
units = dimensionless
- Parameters
-
dlnActCoeffdlnX_diag Output vector of derivatives of the log Activity Coefficients wrt the mole fractions. length = m_kk
Reimplemented from ThermoPhase.
Definition at line 486 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::dlnActCoeffdlnX_diag_, Phase::m_kk, and PhaseCombo_Interaction::s_update_dlnActCoeff_dlnX_diag().
◆ getdlnActCoeffdlnN_diag()
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virtual |
Get the array of log species mole number derivatives of the log activity coefficients.
For ideal mixtures (unity activity coefficients), this can return zero. Implementations should take the derivative of the logarithm of the activity coefficient with respect to the logarithm of the concentration- like variable (i.e. moles) that represents the standard state. This quantity is to be used in conjunction with derivatives of that species mole number variable when the derivative of the chemical potential is taken.
units = dimensionless
- Parameters
-
dlnActCoeffdlnN_diag Output vector of derivatives of the log Activity Coefficients. length = m_kk
Reimplemented from VPStandardStateTP.
Definition at line 478 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::dlnActCoeffdlnN_diag_, Phase::m_kk, and PhaseCombo_Interaction::s_update_dlnActCoeff_dlnN_diag().
◆ getdlnActCoeffdlnN()
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virtual |
Get the array of derivatives of the log activity coefficients with respect to the log of the species mole numbers.
Implementations should take the derivative of the logarithm of the activity coefficient with respect to a species log mole number (with all other species mole numbers held constant). The default treatment in the ThermoPhase object is to set this vector to zero.
units = 1 / kmol
dlnActCoeffdlnN[ ld * k + m] will contain the derivative of log act_coeff for the m-th species with respect to the number of moles of the k-th species.
\[ \frac{d \ln(\gamma_m) }{d \ln( n_k ) }\Bigg|_{n_i} \]
- Parameters
-
ld Number of rows in the matrix dlnActCoeffdlnN Output vector of derivatives of the log Activity Coefficients. length = m_kk * m_kk
Reimplemented from GibbsExcessVPSSTP.
Definition at line 494 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::dlnActCoeffdlnN_, Phase::m_kk, and PhaseCombo_Interaction::s_update_dlnActCoeff_dlnN().
◆ readXMLBinarySpecies()
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private |
Process an XML node called "binaryNeutralSpeciesParameters".
This node contains all of the parameters necessary to describe the Margules model for a particular binary interaction. This function reads the XML file and writes the coefficients it finds to an internal data structures.
- Parameters
-
xmlBinarySpecies Reference to the XML_Node named "binaryNeutralSpeciesParameters" containing the binary interaction
Definition at line 524 of file PhaseCombo_Interaction.cpp.
References XML_Node::attrib(), Phase::charge(), XML_Node::child(), Cantera::getFloatArray(), PhaseCombo_Interaction::m_HE_b_ij, PhaseCombo_Interaction::m_HE_c_ij, PhaseCombo_Interaction::m_pSpecies_A_ij, PhaseCombo_Interaction::m_pSpecies_B_ij, PhaseCombo_Interaction::m_SE_b_ij, PhaseCombo_Interaction::m_SE_c_ij, PhaseCombo_Interaction::m_VHE_b_ij, PhaseCombo_Interaction::m_VHE_c_ij, PhaseCombo_Interaction::m_VSE_b_ij, PhaseCombo_Interaction::m_VSE_c_ij, XML_Node::name(), XML_Node::nChildren(), Cantera::npos, PhaseCombo_Interaction::numBinaryInteractions_, PhaseCombo_Interaction::resizeNumInteractions(), Phase::speciesIndex(), Phase::speciesName(), and Cantera::toLowerCopy().
Referenced by PhaseCombo_Interaction::initThermoXML().
◆ resizeNumInteractions()
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private |
Resize internal arrays within the object that depend upon the number of binary Margules interaction terms.
- Parameters
-
num Number of binary Margules interaction terms
Definition at line 505 of file PhaseCombo_Interaction.cpp.
References PhaseCombo_Interaction::m_HE_b_ij, PhaseCombo_Interaction::m_HE_c_ij, PhaseCombo_Interaction::m_HE_d_ij, PhaseCombo_Interaction::m_pSpecies_A_ij, PhaseCombo_Interaction::m_pSpecies_B_ij, PhaseCombo_Interaction::m_SE_b_ij, PhaseCombo_Interaction::m_SE_c_ij, PhaseCombo_Interaction::m_SE_d_ij, PhaseCombo_Interaction::m_VHE_b_ij, PhaseCombo_Interaction::m_VHE_c_ij, PhaseCombo_Interaction::m_VHE_d_ij, PhaseCombo_Interaction::m_VSE_b_ij, PhaseCombo_Interaction::m_VSE_c_ij, PhaseCombo_Interaction::m_VSE_d_ij, Cantera::npos, and PhaseCombo_Interaction::numBinaryInteractions_.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies().
◆ initLengths()
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private |
Initialize lengths of local variables after all species have been identified.
Definition at line 209 of file PhaseCombo_Interaction.cpp.
References GibbsExcessVPSSTP::dlnActCoeffdlnN_, Phase::m_kk, and Array2D::resize().
Referenced by PhaseCombo_Interaction::initThermo().
◆ s_update_lnActCoeff()
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private |
Update the activity coefficients.
This function will be called to update the internally stored natural logarithm of the activity coefficients
Definition at line 257 of file PhaseCombo_Interaction.cpp.
Referenced by PhaseCombo_Interaction::getActivityCoefficients(), and PhaseCombo_Interaction::getChemPotentials().
◆ s_update_dlnActCoeff_dT()
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private |
Update the derivative of the log of the activity coefficients wrt T.
This function will be called to update the internally stored derivative of the natural logarithm of the activity coefficients wrt temperature.
Definition at line 289 of file PhaseCombo_Interaction.cpp.
Referenced by PhaseCombo_Interaction::getd2lnActCoeffdT2(), and PhaseCombo_Interaction::getdlnActCoeffdT().
◆ s_update_dlnActCoeff_dlnX_diag()
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private |
Update the derivative of the log of the activity coefficients wrt log(mole fraction)
This function will be called to update the internally stored derivative of the natural logarithm of the activity coefficients wrt logarithm of the mole fractions.
Definition at line 458 of file PhaseCombo_Interaction.cpp.
Referenced by PhaseCombo_Interaction::getdlnActCoeffdlnX_diag().
◆ s_update_dlnActCoeff_dlnN_diag()
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private |
Update the derivative of the log of the activity coefficients wrt log(moles) - diagonal only.
This function will be called to update the internally stored diagonal entries for the derivative of the natural logarithm of the activity coefficients wrt logarithm of the moles.
Definition at line 371 of file PhaseCombo_Interaction.cpp.
Referenced by PhaseCombo_Interaction::getdlnActCoeffdlnN_diag().
◆ s_update_dlnActCoeff_dlnN()
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private |
Update the derivative of the log of the activity coefficients wrt log(moles_m)
This function will be called to update the internally stored derivative of the natural logarithm of the activity coefficients wrt logarithm of the mole number of species
Definition at line 408 of file PhaseCombo_Interaction.cpp.
Referenced by PhaseCombo_Interaction::getdlnActCoeffdlnN().
Member Data Documentation
◆ numBinaryInteractions_
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protected |
number of binary interaction expressions
Definition at line 545 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_HE_b_ij
|
mutableprotected |
Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 549 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_HE_c_ij
|
mutableprotected |
Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 553 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_HE_d_ij
|
mutableprotected |
Enthalpy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 557 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::resizeNumInteractions().
◆ m_SE_b_ij
|
mutableprotected |
Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 561 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_SE_c_ij
|
mutableprotected |
Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 565 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_SE_d_ij
|
mutableprotected |
Entropy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 569 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::resizeNumInteractions().
◆ m_VHE_b_ij
|
mutableprotected |
Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 573 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_VHE_c_ij
|
mutableprotected |
Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 577 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_VHE_d_ij
|
mutableprotected |
Enthalpy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 581 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::resizeNumInteractions().
◆ m_VSE_b_ij
|
mutableprotected |
Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 585 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_VSE_c_ij
|
mutableprotected |
Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 589 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_VSE_d_ij
|
mutableprotected |
Entropy term for the quaternary mole fraction interaction of the excess Gibbs free energy expression.
Definition at line 593 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::resizeNumInteractions().
◆ m_pSpecies_A_ij
|
protected |
vector of species indices representing species A in the interaction
Each Margules excess Gibbs free energy term involves two species, A and B. This vector identifies species A.
Definition at line 600 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ m_pSpecies_B_ij
|
protected |
vector of species indices representing species B in the interaction
Each Margules excess Gibbs free energy term involves two species, A and B. This vector identifies species B.
Definition at line 607 of file PhaseCombo_Interaction.h.
Referenced by PhaseCombo_Interaction::readXMLBinarySpecies(), and PhaseCombo_Interaction::resizeNumInteractions().
◆ formMargules_
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protected |
form of the Margules interaction expression
Currently there is only one form.
Definition at line 613 of file PhaseCombo_Interaction.h.
◆ formTempModel_
|
protected |
form of the temperature dependence of the Margules interaction expression
Currently there is only one form -> constant wrt temperature.
Definition at line 619 of file PhaseCombo_Interaction.h.
The documentation for this class was generated from the following files:
